TRANSITION-METALS AS CATALYSTS OF AUTOXIDATION REACTIONS

被引：636
作者：
MILLER, DM [1 ]
BUETTNER, GR [1 ]
AUST, SD [1 ]
机构：
[1] UTAH STATE UNIV,DEPT CHEM & BIOCHEM,LOGAN,UT 84322
来源：
FREE RADICAL BIOLOGY AND MEDICINE | 1990年 / 8卷 / 01期
关键词：
Autoxidation; Chelation; Free radicals; Hydroxyl radical; Iron; Peroxidation; Superoxide;
D O I：
10.1016/0891-5849(90)90148-C
中图分类号：
Q5 [生物化学]; Q7 [分子生物学];
学科分类号：
071010 ; 081704 ;
摘要：
Superoxide (O2 - ̇, hydrogen peroxide (H2O2), and hydroxyl radical (·OH) produced from the "autoxidation" of biomolecules, such as ascorbate, catecholamines, or thiols, have been implicated in numerous toxicities. However, the direct reaction of dioxygen with the vast majority of biomolecules, including those listed above, is spin forbidden, a condition which imposes a severe kinetic limitation on this reaction pathway. Therefore, an alternate mechanism must be invoked to explain the "autoxidations" reactions frequently reported. Transition metals are efficient catalysts of redox reactions and their reactons with dioxygen are not spin restricted. Therefore it is likely that the "autoxidation" observed for many biomolecules is, in fact, metal catalyzed. In this paper we discuss: 1) the quantum mechanic, thermodynamic, and kinetic aspects of the reaction of dioxygen with biomolecules; 2) the involvement of transition metals in biomolecule oxidation; and 3) the biological implications of metal catalyzed oxidations. We hypothesize that true autoxidation of biomolecules does not occcur in biological systems, instead the "autoxidation" of biomolecules is the result of transition metals bound by the biomolecules. © 1990.
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页码：95 / 108
页数：14
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